Production of colored colloid layers



Patented Oct. 30, 1951 PRODUCTION OF COLORED COLLOID LAYERS Ronald Bernard Collins, Harry Derek Edwards,

and Oliver Edmund Pratt, Ilford, England, as-

signors to Ilford Lim British company ited, Ilford, England, a

No Drawing. Application May 7, 1946, Serial No. 667,990. In Great Britain May 15, 1945' Claims. (01. 117-34) This invention relates to the production of coloured colloid layers and particularly to the production of such layers as elements in lightsensitive photographic materials.

Photographic materials frequently include, in addition to a support layer and one or more light-sensitive layers, a coloured colloid layer which serves to prevent halation, i. e. a socalled anti-halation layer. Where the support is transparent this is usually coated on the side of the support remote from the emulsionlayer, but if the element is intended to be exposed through the support the anti-halation layer may be applied to the outer surface of the light-sensitive layer. Where the support is not transparent the anti-halation layer is usually coated between the light-sensitive layer and the support.

Further, many photographic materials, especially those used for colour photography, include coloured colloid layers between emulsion layers, such layers serving as light filters.

It is of particular importance, especially where such coloured colloid layers are coated adjacent to light-sensitive layers, that the colouring material employed should not diffuse from the coloured colloid layer into any adjacent layer of the Photographic material.

The present invention provides a method of producing coloured colloid layers which may serve as anti-halation or filter layers and which are strongly resistant to such diffusion, and inaddition provides a method whereby an originally colourless colloid layer of the photographic material may be converted, when required, to a thereafter applying to such layer an aqueous solution of a dyestuff which has an opposite electrostatic charge to that carried by the said surface-active agent.

More specifically, according to this invention, (a) a water-permeable colloid layer containing an anion-active agent is treated with an aqueous solution 'of a basic dyestufi; or (b) a waterpe'rmeable colloid layer containing a Ration-- active agent is treated with an aqueous solution of an acid dyestufl'.

It is found that, under the conditions specified, the dyestuff is firmly held in the layer and is not removed by prolonged washing in water.

boxylic acids, e. g. soluble salts of fatty acidscontaining eight or more carbon atoms, as, for example, oleic, ricinoleic, linoleic, stearic and palmitic acids. less preferable than (b) Soluble salts of long-chain alkyl sulphonic acids,

(c) Soluble salts of sulphated higher fatty alcohols, e.- g. soluble salts of fatty alcohol sulphates of which the alkyl group contains at least; eight :carbon atoms, as, for example, the

soluble salts of lauryl hydrogen sulphate and oleyl hydrogen sulphate,

(d) Soluble salts of sulphated secondary alcohols containing at. least eight carbon atoms in the chain,

(c) Soluble salts of alkylated aromatic sulphonic acids, e. g. soluble salts of alkyl benzene "sulphonic acids, of alkyl naphthalene sulphonic acids and of alkylated hydroxy diphenyl sulphonic acids,

(f) Soluble salts of long-chain alkyl esters of succinic acid.

The soluble salts may be formed from alkali metals, e. g. sodiumand potassium, from ammonium or from amines, e. g. triethanolamine and cyclohexylamine.

The compounds may contain amino residues in the "anion, as for example in the sodium salt of oleoyl, amino ethanesulphonic acid which contains a carbonamide group (-NH.CO 5

very manyaniomactiveagents are commer f cially marketed as detergents and these commerfcia1 products may conveniently b employ-ed These, however, are generally.

the process of this invention. Thus, suitable commercial products are those sold under the trade names:

Trade Name Believed to be Aerosol OT the sodium salt of a sulphated dicarboxylic ester. Agral N the sodium salt of an alkyl naphthalene sulphonic acid.

Similarly the strength of the dye solution applied to the layer may vary widely, but generally solutions of /2 to 2% strength are suitable.

The following examples illustrate the invention:

EXAMPLE 1 An 8% solution of gelatin in water was prepared, and to portions of it was added a range of quantities of Teepol X. The resulting solutions were coated on photographic film base and dried. The sample coatings thus prepared were then bathed in a /2% solution of Auramine 0 (colour index No. 655) for periods of one to eight minutes, and'then washed for one hour in running water and dried. The density of the dye-layers was-then determined and the following results were obtained;

Do. I the sodium salt of an alkyl benzene sulphonicacid. triethanolamine dodecyl sulphatei ammonium dodecyl sulphate. cyolohexylamine dodecyl sulphate.

Santomerse D.

Sulphonated Lorol TA Sulphonated Lorol NH. Sulphonated Lorol CY Sulphonated Ocenol. a sulphonated fatty alcohol.

Teepol a sodium alkyl sulphate.

Tergitol ,4... a sodium secondary alkyl sulphate. Ter'gitol 7 Do.

Kation-active agents which maybe employed are, for example, alkyl-, aryland aralkylsubstituted ammonium compounds and quaternary salts of hetero'cyclic nitrogen compounds. Specific examples are dodecyl pyridinium sulph'ate, cetyl py'ridiiiium bromide and the materials sold under the trade names'LissolamineA (believed to be cetyl trimethyl ammonium bromide), Sap'amine' MSibelieve'd to be a diethyl aminoethyl long-chain alkyl amide ester), Fixan'olC believedto be'c'etyl pyridinium bromide) and octadecylamine.

The water-permeable colloid layer which is to be coloured maybe composed of gelatin, casein, agar-agaror other natural material, or may be a synthetic polymeric material such as a polyvinyl acetate having a low degree of esterifica'tion or a partially hydrolysed methyl methacrylate resin, or may be a water-permeable cellulose ether'or cellulose ester, e. g. cellulose acetate, having a" low degree of esterification.

Large numbers of acid dyes'a'nd'basic dyes are well known an'd'describe'd in Rowes colour index, and it is unnecessary to list them. The follow ing' are, however, examples of th type of dye stufi which may be employed:

The proportion of surface-active agent added to}: the colloid layer may vary over a wide range according to the results desired, but generally speaking will not exceed 50% of the total-weight of the colloid-layer and will usually be much' less Table 1 Time (in minutes) of bathing in Auramine 0 Solution Concentration of Teepol X in ccs. per

100cc. 8% gelatin solution o Table 2 Time (in minutes) of bathing in Tar- Concentratwn oi Lissolamine A'in gms. trazine Solution per 100 cc. of 8% gelatin EXAMPLE 3 using octadecylamine hydrochloride as the sur-' face-active agent and Tartrazine as the dye. The following-density figures were obtained:

0 Table 3 7 Time (in minutes) of bathing in 34% Tar- Concentration of Octadecylaminehydro- Mine Solution:

chloride in gms. perlOO cc.'of 8% gelatin 8011113011 EMAMPLE 4:"

Theproce'dure-of Example. Lwasefollowedusing Dispersol L as. the sumac-active agentrandusing Lissolamine A as the surface-active'agentl The procedure of Example 1 was followed;

ouxio OWN Auramine as the dye. The following densities were obtained:

Table 4 bathing in Aura- Concentration of Dispersol L in ccs. per mine Solution 100 cc. of 8% gelatin solution EXAMPLE TabFe 5 Time (in minutes) of bathing in Au- Concentration of Sodium dodecyl sulramine 0 Solution phate in gms. per 100 cc. of 8% gelatin solution NNB'H man o It will be observed from the density figures given in the foregoing examples that, whilst after an hours washing a strong density of dyestuff is held in the layers containing the sur face-active agents, virtually none of the dye remains in a similar layer not containing the surface-active agent.

The density figures in the foregoing examples were determined in a standard type densitometer, the specimens being viewed through a filter transmitting only between 3800 A. and 5000 A.

The surface-active agents are themselves usually colourless and the invention therefore affords a method of producing a photographic material in which one or more layers containing surface-active agents are present and are initially colourless but can be coloured at any desired stage in'the processing of the material.

What we claim is:

1. A method of forming a photographic element comprising a film support and a Waterpermeable coloured colloid layer which comprises (1) coating a film support with a layer of a water-permeable colloid containing an uncoloured salt selected from the group consisting of (a) anion-active alkali metal, ammonium and amine salts of long chain sulphonic and sulphuric acids which contain an alkyl radical of at least 8 carbon atoms in the anion, and (b) cation-active alkyl substituted ammonium salts and quaternary salts of heterocyclic nitrogen compounds each of which contains a long chain alkyl radical of at least 8 carbon atoms in the cation, and thereafter (2) applying to such layer an aqueous solution of a dye, a basic dye being selected when the uncoloured salt is anion-active and an acid dye being selected when the uncoloured salt is cation-active, thereby forming in said colloid layer a relatively stable, water insoluble dye complex between-said dye and said salt.

2. A method of forming a photographicelement comprising a film support, a water-permeable coloured colloid layer and a light-sensitive colloid-silver halide layer which comprises (1) Time (in minutes) vof 7 6 coating a film support with a layer of a waterpermeable colloid containing an uncoloured salt selected from the group consisting of ('a) anionactive alkali metal, ammonium and amine salts of long chain sulphonic and sulphuric acids which contain an alkyl radical of at least 8 carbon atoms in the anion, and (b) cation-active alkyl substituted ammonium salts and quaternary salts of the heterocyclic nitrogen compounds each of which contains a long chain alkyl radical of at least 8 carbon atoms in the cation, and thereafter (2) applying to such layer an aqueous solution of a dye, a basic dye being selected when the uncoloured salt is anion-active and an acid dye being selected when the uncoloured salt is cationactive, thereby forming in said colloid layer a relatively stable, water-insoluble dye complex between said dye and said salt, and applying a light-sensitive colloid silver halide layer thereto.

3. A method of forming a photographic element comprising a film support and a waterpermeable coloured colloid layer which comprises coating a film support with a layer of a water-permeable colloid containing an uncoloured anion-active alkali metal salt of an aliphatic sulphonic acid containing an alkyl radical of at least 8 carbon atoms in the anion, and thereafter applying to such layer an aqueous solution of a basic dye, thereby forming in said colloid layer a relatively stable, water-insoluble dye complex between said dye and said salt.

4. A method of forming a photographic element comprising a film support and a waterpermeable coloured colloid layer which comprises coating a film support with a layer of a waterpermeable colloid containing an uncoloured anion-active alkali metal salt of an alkyl sulphate containin an alkyl radical of at least '8 carbon atoms in the anion, and thereafter applying to such layer an aqueous solution of a basic dye, thereby forming in said colloid layer a relatively stable, water-insoluble dye complex between said dye and. said salt.

5. A method of forming a photographic element comprising a film support and a waterpermeable coloured colloid layer which comprises coating a film support with a layer of a water-permeable colloid containing an uncoloured cation-active alkyl-substituted ammonium salt containing an alkyl radical of at least 8 carbon atoms in the cation, and thereafter applying to such layer an aqueous solution of an acid dye, thereby forming in said colloid layer a relatively stable, water-insoluble dye complex between said dye and said salt.

RONALD BERNARD COLLINS. HARRY DEREK EDWARDS. OLIVER EDMUND PRATT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A METHOD OF FORMING A PHOTOGRAPHIC ELEMENT COMPRISING A FILM SUPPORT AND A WATERPERMEABLE COLOURED COLLOID LAYER WHICH COMPRISES (1) COATING A FILM SUPPORT WITH A LAYER OF A WATER-PERMEABLE COLLOID CONTAINING AN UNCOLOURED SALT SELECTED FROM THE GROUP CONSISTING OF (A) ANION-ACTIVE ALKALI METAL, AMMONIUM AND AMINE SALTS OF LONG CHAIN SULPHONIC AND SULPHURIC ACIDS WHICH CONTAIN AN ALKYL RADICAL OF AT LEAST 8 CARBON ATOMS IN THE ANION, AND (B) CATION-ACTIVE ALKYL SUBSTITUTED AMMONIUM SALTS AND QUATERNARY SALTS OF HETEROCYLIC NITROGEN COMPOUNDS EACH OF WHICH CONTAINS A LONG CHAIN ALKYL RADICAL OF AT LEAST 8 CARBON ATOMS IN THE CATION, AND THEREAFTER (2) APPLYING TO SUCH LAYER AN AQUEOUS SOLUTION OF A DYE, A BASIC DYE BEING SELECTED WHEN THE UNCOLOURED SALT IS ANION-ACTIVE AND AN ACID DYE BEING SELECTED WHEN THE UNCOLORED SALT IS CATION-ACTIVE, THEREBY FORMING IN SAID COLLOID LAYER A RELATIVELY STABLE, WATER INSOLUBLE DYE COMPLEX BETWEEN SAID DYE AND SAID SALT. 